Process of precipitating h2tio3

ABSTRACT

THIS APPLICATION DISCLOSES THE PRECIPITION OF H2TIO3 FROM AN ACID SOLUTION OF TITANYL SULFATE BY MIXING SAID SOLUTION WITH AN ALKALINE SOLUTION UNDER CONIDTIONS OF HIGH SHEAR, REMOVING SAID H2TIO3 AND DRYING SAME.

Sept- 5, 1972 w. L. CRAIG 3,689,219

PROCESS 0F PRECIPITATING H2Ti05 WILLIAM L. CRAIG TOR/JEVS Sept. 5, 1972 Original Filed March 29, 1965 4 Sheets-Sheet 2 A ORNEYS Sept. 5, 1972 w. L. CRAIG PROCESS OF PRECIPITATING HZTOB original Filed Mann 29. 1955 4 Sheets-Sheet 3 SOLUTION C SOLUTION B SOLUTION A TO STORAGE INVENTOR.

wlLLlAM L. CRAIG Ar ORNEYS FLOW Sept 5 197? w. L. CRAIG 3,689,219

PROCESS OF PRECIPITATING H2TiO,`5

Original Fled March 29, 1965 4 Sheets-Sheet 4 PERCENT TRANSMITTANCE (AT SOOmU) INVENTOR. WILLIAM L. CRAIG A roR/VE Ys ABSTRACT F THE DISCLOSURE This application discloses the precipitation of H2Ti03 from an acid solution of titanyl sulfate by mixing said solution with an alkaline solution under conditions of high shear, removing said H2TiO3 'and drying same.

This is a divisional application of Ser. No. 447,116, led Mar. 29, 1965 now U.S. 3,528,836, issued Sept. l5, 1970. This application is a continuation of Ser. No. 850,282, led June l1, 1969, now abandoned.

This invention relates to pigments or iillers containing titanium dioxide, and to procedure and materials used in making such pigments.

Titanium dioxide has been used in the paper industry for many years as an opacifying pigment. One of the problems connected with the use of this pigment in a paper mill system is the requirement that the pigment be nely dispersed and uniformly distributed throughout the paper. Titanium dioxide particles are manufactured having mean particle size of about 0.25 micron. This particle size is carefully controlled by the manufacturer to produce the maximum light reflectance or opacity. When the pigment is used in a paper mill system it is diflicult to maintain the proper dispersion because the small paritcles of T iO2 must be ilocculated in order to retain them in the iiber matrix. Such occulation or piling reduces the desired optical efficiency of the titanium dioxide pigment.

The dispersion problem has been studied by pigment chemists for many years in an attempt to obtain a better pigment for the paper industry. Various pigment extensions were made by physically blending TiOZ with other inorganic compounds such as barium sulfate, calcium sulfate, calcium silicate, aluminum silicate and hydrated silicates. Such extended pigments were used throughout the paper industry for many years. However, the purchase of such materials is not favored because in some instances it has been found more economical merely to blend the individual components of the mixture at the paper mill.

Similarly, in the paint, rubber and other fields, TiOZ has been blended with extenders such as CaSO4, BaSO4, aluminum silicates to reduce the cost of the material. Such extenders serve to keep the Ti02 particles separated in the matrix and reduce piling which, in turn, produces a higher degree of optical etliciency from the TiO2. Although the physical extension of the TiOZ particles does in some measure increase the opacity of the material such as the finished sheet of paper, rubber, paint film, etc. the efficiency of the Ti02 particles is still far fbelow their maximum capabilities.

In accordance with the present invention there is produced a complex composition consisting essentially of TiO2, Si02 and CaO made by precipitation from an acid solution of titanyl sulfate containing calcium ions and silicate ions dissolved therein, by mixing such solution with an yalkaline solution under conditions of high shear. According to a particular embodiment of the invention, there is produced a complex composition consisting essentially of TiO2, SiO2, CaO and barium sulfate made by precipitation from an acid solution of titanyl sulfate con- 'United States Patent ice taining calcium ions and silicate ions dissolved therein, by mixing such solution with an alkaline solution containing barium ions dissolved therein under conditions of high shear. A novel aspect of the invention is the aqueous acid solution of titanyl sulfate containing calcium and silicate ions dissolved therein, which upon being neutralized with an alkali precipitates the complex Ti02, SiO2 and CaO. As the term is used in the specification and claims, TiO2 includes both the anhydrous form and TiOZ in the form of the hydrate H2Ti03.

According to the method of the invention the complexes are preferably produced by continuously introducing into a high shear zone adjacent a rapidly rotating impeller, an aqueous acid solution of titanyl sulfate containing the calcium and silicate ions dissolved therein, and simultaneously continuously introducing into said zone an aqueous alkaline solution of an alkali metal (suitably containing the barium ion dissolved therein if desired) in an amount suflicient substantially to neutralize said titanyl sulfate solution, and preferably raise the pH to a value between about 8 and l0, thereby to precipitate the desired complex. The effluent containing said precipitated complex is continuously withdrawn from the high shear zone.

The slurry containing the complex dispersed in the mother liquor is then filtered or centrifuged to recover the complex, which is thereafter dried, calcined and ground to produce the pigment having the desired particle size and suitably dispersed particles. The precipitated complex pigment will have an average particle size not greater than 0.5 micron, preferably, under optimum conditions, not greater than about 0.25 micron.

In the case of pure TiO2, there is a rather critical particle size range needed to obtain maximum opacity, i.e., about 0.2-0.25 micron. With my extended pigment, however, made by the procedures described herein, and containing at least about 25% of extending material, the permissible particle size range s about 0.15 to 0.5 micron for maximum opacity. The preferred amount of extender is about 60-70%, that is, about S0-40% TiO'2.

It has been found that upon calcining the TiO2 or the TiOZ complex obtained according to the invention, a TiOz pigment is obtained (without seeding) which has a substantially higher rutile content as compared with Ti02 pigments obtained by ordinary sulfuric acid procedures (without seeding). Therefore, a particular aspect of the invention resides in the method of producing a TiO2 pigment having increased rutile content by the sulfuric acid process, even in the absence of CaSiO3 and BaSO4, by carrying out the process described under conditions of high shear, preferably by continuously introducing into a high shear zone adjacent a rapidly rotating impeller, an aqueous acid solution of titanyl sulfate, simultaneously continuously introducing into said Zone an aqueous alkaline solution of an alkali metal in an amount sufficient substantially to neutralize said titanyl sulfate solution and preferably raise the pH to a value in the range of about 8-10, thereby to precipitate H2Ti03, continuously withdrawing from the zone the eluent containing the precipitated H2Ti03, which is then removed from its mother liquor, dried and calcined to produce TiOg. The calcining is carried out under known conditions.

FIG. l is an X-ray diffraction diagram of a TiO2 pigment made according to the invention;

FIG. 2 is another X-ray diffraction diagram of a Ti02 pigment made according to the invention;

FIG. 3 is still another X-ray diffraction diagram of a TiOZ pigment made according to the invention;

FIG. 4 is a diagrammatic section of a portion of a centrifugal pump useful in carrying out the process of the invention;

FIG. is an enlarged drawing of a portion of the pump shown in FIG. 4;

FIG. 6 is a diagrammatic section of the pump shown in FIG. 4 taken along the axis of the impeller; and

FIG. 7 is a diagram showing light absorption of water suspensions made according to the invention.

It is not known exactly why the conditions set forth above produce the unexpected results that have been found. It is thought, however, that as the alkaline solution, suitably containing the barium ion, combines with the strongly acid titanyl sulfate solution, the following reactions may occur instantaneously and simultaneously:

(1) The titanyl sulfate instantly hydrolyzes to titanic acid (HZTiOa).

(2) The barium salt (if present) reacts with the available sulfate ions and forms an insoluble barium sulfate and the calcium ion combines with Si02 to form the hydrated calcium silicate. It is noted that under these conditions calcium sulfate cannot be formed since it is soluble.

(3) The control of the extent of shear at the point of mixing and precipitation is believed to be important. The two major controlling factors for this formation are ternperature and agitation. By maintaining the rate of shear at its maximum value and the temperature at its optimum value, the ultimate neness of the discrete particles as formed is assured.

(4) The fact that all the chemical constituents involved in the reaction are soluble and ionized permits simultaneous double decomposition of the salts to form the insoluble complex structure.

The ratio of TiO-z to the other components of the complex may be varied over a wide range. In fact, substantially pure TiO2 may be made utilizing the present invention. The content of barium sulfate and calcium silicate will depend generally upon the use to be made of the pigment. For reasons of economy it will be desired to include as much calcium silicate and barium sulfate as can be tolerated since they are relatively less expensive materials. A suitable range of TiOz content for the extended pigment is about 5 to 95%, preferably about 5 to 40% TiO2 based on the total weight of the complex, the remainder representing the content of CaO, SiO2 and BaSO4, (if present).

The ratio of the barium sulfate to the calcium silicate may also be varied, suitably within the range from about 95:5 to 5:95 by weight. Since the BaSO., is a dense material and the hydrated calcium silicate is a relatively less dense and bulky material, it is preferred, particularly from the standpoint of the fired product, to balance these characteristics of the two materials. The preferred amounts are about equal on a weight basis but acceptable qualities may be obtained in the range of about 30:70 to 70:30 of the two materials.

The techniques useful in controlling the precipitation of the pigment and the characteristics of the precipitated pigment include temperature, pH, water dilution and degree of shear. The temperature within the zone of high shear where precipitation occurs, is preferably elevated, thereby to make the reaction go more rapidly. Temperatures within the range of about G-212 F. are suitable, but they are preferably in excess of 170 F.

The temperature of a titanyl sulfate solution before it reaches the zone of high shear, however, is governed by other factors. Excessively high temperatures will cause the titanyl sulfate to hydrolyze prematurely and the titanium to precipitate. Accordingly, the temperature of the titanyl sulfate solution is maintained below the thermal hydrolysis temperature, which is about 170 F.

The titanyl sulfate solution will, of course, be strongly acid. The pH will generally be about 1.0 or less, and low enough to keep the titanium and the calcium and the silicate to be added, in solution. The calcium chloride solution and the sodium silicate solution are added to the strongly acid titanyl sulfate solution and the components are mixed together. Although the solution is concentrated with respect to sulfuric acid, the TiO2 content is only about 20%, that is about 0.3 gram per cubic centimeter. The solution is then diluted with water, preferably hot water, to reduce the TiO2 concentration to below about 10%, preferably about 2% or lower. The diluted hot solution is added as soon thereafter as practical to the high shear zone.

Although the reaction may be carried out using the concentrated titanyl sulfate solution, the dilution affords easier control of the reaction to produce the desired product.

The type of sodium silicate employed is not critical. However, it is preferred to use a sodium silicate that has a high SiOZ content, inasmuch as it is the Si02 which will appear in the nal product. A suitable material is NazO- 3 to 4 SiO2. Other alkali metal silicates, such a potassium silicate may be used. The use of calcium chloride is not critical and, in fact, other soluble and compatible calcium salts may be used.

The ratiod of CaO to SiO2 in the final complex will depend, of course, upon the ratio of calcium to silicate added to the titanyl sulfate solution. This is a factor which is subject to wide variation depending upon the qualities desired in the final product. For example, the more dense CaSiO3, in which the ratio of CaO to SiO2 is 1:1 may be formed. This may provide advantages, particularly where little or no BaSO4 is present. It is preferred, however, to have a relatively high ratio of SiO2 to CaO, that is above about 3:1, which is a less dense and more bulky material.

Although sodium hydroxide is preferred for reasons of economy, other strong alkalies, particularly alkali metal alkalies such as potassium hydroxide may be used. The temperature of the caustic solution before it reaches the mixing zone is not critical unless barium salt is present. In the latter event, the time and the temperatre of the alkaline solution containing the barium salt are controlled between the point of mixing the barium salt with the alkali and the high shear precipitating zone to prevent precipitation of barium hydroxide. Preferably the barium salt is added just before the zone of high shear, and the temperature of the alkaline solution is maintained at about 180-200 F. Barium chloride is preferred but other soluble and compatible barium salts may be used.

The following examples are presented to illustrate the invention, the parts expressed being on a weight basis unless otherwise indicated.

EXAMPLE l One source used for the titanium was a titanium bearing iron slag known as Sorel slag. This slag contains about 75% Ti02 and approximately 8% iron (FeO). The following components and materials were used in preparing the ore:

The ore was ground in a ball mill to a neness that would pass through a 200 mesh screen. The correct amount of ground ore was then placed in a three-necked flask and the concentrated sulfuric acid was added to the flask. A mercury seal agitator system was inserted in the center neck of thc flask, a water condenser in another neck of the flask, and a 400 C. thermometer in the remaining neck of the ask. The sulfuric acid Ilmenite slurry was heated under constant agitation to C. At this point the dextrin was added to prepare for the exothermic reaction. The heating was continued until a temperature of 220 C. was reached at which point the slurry formed into a solid cake. The cake was allowed to cool to 60 C. and the correct amount of 0.1 N H2804 was added to the flask and the cake was dissolved into solution. The correct amount of As203 was then added and allowed to mix for 15 minutes. Then the FeS was added and mixed well for 30 minutes. The arsenic and the iron treatments were used to aid in the clarification of the liquid. About 2 liters of distilled water were added to the mixture to assist in filtering, and the liquid was filtered in a Buchner system with an acid filter paper to remove undigested sludge.

At this point the titanium and iron were in complete solution and the liquor was ready for the next processing step. The iron in the liquor (as ferrous sulfate) was completely soluble in extreme dilutions, whereas the titanyl sulfate hydrolyzeson dilution to H2Ti03 which is an insoluble precipitate. Therefore the iron was removed by the following procedure.

One volume of the liquor was slowly added to ten volumes of boiling water, the titanyl sulfate instantly hydrolyzed to titanic acid (H2Ti03). The mixture was filtered and thoroughly washed in a Buchner system. The filtrate contained the ferrous sulfate and was discarded. An amount of sulfuric acid equal to the sulfuric acid content of the original liquor was slowly added to the wet filtered cake of H2TiO3 in a 4 liter beaker, a little bit at a time under continuous mixing. The heat of the solution is usually sufficient to raise the temperature to approximately 125 C. at which point the titanic acid reverts to the titanyl sulfate; if not, heat is added slowly while mixing continuously. At this point the liquor was purified and contained only titanyl sulfate. This liquor was referred to as black liquor. It contained the equivalent of about 0.144 gram of Ti02 per milliliter and at this point was ready to receive the other inorganic chemicals in preparation for the final precipitation of the complex. Other procedures known in the prior art may be used for preparing the purified (iron free) black liquor.

1200 millilters of water at 140 F. were added to 42 ml. of the black liquor; 30 ml. of a calcium chloride solution CaClz by volume) were then added; 40 ml. of a sodium silicate solution (18.5% Nago-3.25 Si02 by volume) were added to complete the black liquor preparation. This solution was strongly acidic and contained titanium, silicon dioxide and calcium, all in solution in the sulfuric acid. The black liquor was now ready to be precipitated to produce the desired complex pigment.

To 1600 ml. of water at 200 F. were added 53.6 ml. of a barium chloride solution (10% BaCl2 by volume). 215 ml. of 5 N NaOH solution was prepared. The diluted black liquor solution (1312 ml.) was placed in a high shear reactor, that is a Waring type commercial blender Model CB-3, 1 gallon capacity, 14,500 r.p.m., V2 HP. The black liquor in the reactor was placed under high shear and the 5 N caustic solution was quickly added to the barium chloride solution and this mixture was added as fast as possible to the reactor. This technique produced an instantaneous reaction with all of the available compounds and the insoluble pigment precipitate was thereby formed. The precipitated pigment was thoroughly washed and filtered in a Buchner system and dried in a low ternperature oven (175 E).

The pigment was refined as follows. After the reacted pigment was thoroughly washed and dried, it ywas ground in a hammermill to reduce the agglomerates to an optimum particle size. The grinding was controlled to produce a pigment having less than 0.1% grit on a 325 mesh screen. Samples of the pigment were calcined in a furnace to determine the optical properties of the particle after loss of the Water of crystallization. Firing is suitably carried out in a mufiie furnace from 400 to 2200 F. preferably at about 1800 F. All of the combined water ignition loss) was removed at temperatures below 600 F. The calcined samples were again ground in the hammermill to the above-mentioned specification. The properties indicated in the following table are those of the uncalcined pigment before the refinement procedure.

G. E. brightness-+ Loss on ignitionapproximately 15% Assay-approximately 33% TiO2 (as H2Ti03), 33% CaO.4SiO2.xH2O (where x varies between 3 and 4), 33% BaSO4 Handsheets of paper were made and tested in accordance with the following procedure.

A sufficient amount of 3% consistency bleached sulphite stock (about 350 C.S.\F. TAPPI Specification T227m-58) to contain 20 gm. of bone dry fiber was weighed out and put under agitation. To this concentrated stock there was added 4 cc. of a 5% rosin size solution (1% on the weight of the fiber), a sufficient amount of the ground pigment slurry to contain 1.2 gm. of dry pigment (6% on the weight of the fiber), and 8 oc. of a 5% iron-free alum solution (2% on the weight of the fiber) in that order, allowing 15 minutes of mixing after each addition. This concentrated stock was diluted to a total volume of 7,600 cc. in a large pail with filtered tap Water and the pH was adjusted to 4.0-4.5 with 1% sulfuric acid. 590 cc. aliquots of this stock were put under mild agitation and 7.5 cc. (1 pound/ton based on 1.5 gm. of fiber) of a 0.01% Vanzak RA (a high molecular weight synthetic polymer cationic retention aid) solution was added and allowed to mix slowly for 2 minutes. The stock was then added to the mold, the pH adjusted to 4.0-4.5 with a 1% sulfuric acid solution, and the handsheets prepared following TAPPI conditions. The sheets were pressed, dried and conditioned overnight before testing. The TAPPI brightness of the sheets and the opacity of the sheets were measured and found to be acceptable.

EXAMPLE 2 The black liquor was prepared according to the procedure described in Example 1 and contained 0.106 gm. of Ti02 per ml.; 1200 ml. of water at 140 F. were added to rnl. of the black liquor; 5 ml. of a calcium chloride solution (10% CaCl2 by volume) were then added; 7 ml. of a sodium silicate solution (18.5 Na2O.3.25 Si02 by volume) were added to complete the black liquor preparation. This solution was strongly acidic and contained the titanium, silicon dioxide and calcium, all in solution in the sulfuric acid. The following procedure was used to initiate the formation of the precipitated pigment.

(l) 9 ml. of a barium chloride solution (10% BaClZ by volume) were added to 250 ml. of water at 130 F.

(2) 1100 ml. of 5 N NaOH solution were added to 500 ml. of distilled water and the solution was heated at 200 F.

(3) The treated black liquor solution was placed in a high shear reactor of the Waring type described in Examp e 1.

(4) The black liquor in the reactor was placed under high shear, that is the agitator of the blender was operated at maximum speed and the 5 N caustic solution along with the barium chloride solution were added simultaneously to the reactor.

The foregoing procedures produced an instantaneous reaction with all of the available compounds and the insoluble pigment particles were formed at the prevailing pH which was about 10.0. The precipitated pigment was thoroughly washed and filtered on a Buchner system and dried at a low temperature hot air circulated oven (175 F). The pigment was ground in a mortar and pestle to a relatively fine particle size. Samples were then calcined in a furnace to determine the optical properties of the particles after the loss of the water of crystallization. The calcined samples were then wet-ground in a ball mill for 72 hours. The grit was controlled to produce a pigment having less than 0.1% grit on a 325 mesh screen.

Handsheets were prepared according to the procedure described in Example 1. The results are presented in the following Table I (under the heading Test No. 2) together with similar data obtained by using other TiOg pigments.

TABLE I Test number Con- 80% T102, trol CaO,

3.8 SiOz 100% T102 10% BaSOr Ti02 pH at preparation 11.0 11.0 Firing temperature, F l 1, 60D 1, 600 Handsheet stock (l) (l) (1) 1 l 1 2 2 6 6 6 (2) (2) (2) 4. 1 4. 1 4. 1 p 4. 2 4. 2 4. 2 Handsheet tests:

Basis Weight (25-3S-500) 43. 6 52. 2 48. 4 TAPPI brightness- 75. 4 79. 1 75. 9 TAPPI opacity 86. E 88. 1 87. 7 Percent T102 in sheet. 4. 43 3. 65 4. 33 Determination ot the pigment ecieney value:

SX value 2.83 3. 27 3.01 Corrected SX value (50 lb. basis Weight) 3.10 3. 14 3. 12 Corrected opacity (5o 1b. basis Weight 88. 6 87. 2 88. 4 Pigment efficiency value 700 8. 60 720 l Bleached sulphite.

2 1 1b.]ton based on 1.5 gm. 0i berweight. Test No. 1 is a pure TiOz prepared from the original black liquor by mixing the black liquor with boiling water with moderate agitation. Test No. 3 is a product prepared in the same way as Test No. 2 (high shear mixing) with the exception that no calcium chloride, sodium silicate or barium chloride were added.

The data appearing at the lower part of Table I under the heading Determination of The Pigment Efciency Value are calculated values to correct for differences in the basis weight of the three samples. The conversions were made by standard procedures as follows:

By the standard procedure described in TAPPI Standard T425m Opacity of Paper, using a Bausch & Lomb Opacimeter, the reiiectance over black R0, and the TAPPI opacity, 0,89, were measured on the paper. Using the Kubelka and Munk chart, the intersect of these values was located and the scattering coeiiicient SX was obtained. Also using standard procedure, the basis weight was corrected to exactly 50 pounds and the new SX value was obtained. The percent titanium dioxide was determined on the basis of the ash content of the papersThc Pigment Eticiency Value was then calculated according to the following formula:

SX Percent T102 in sheet EXAMPLE 3 Following the procedure described in Example l a composite pigment was made containing 38% Ti02, 31% BaSO., and 31% CaO.4SiO2.

The product of Example 3 and two of the products from Example 2, that is Tests Nos. 2 and 3, were examined by X-ray ditfraction using a standard Norelco high angle automatic ditractometer, utilizing nickel filtered Pigment eciency value:

copper radiation, The charts obtained are presented herewith an FIGS. l, 2 and 3. The instrument operated at 40,000 volts, and 20 milliamps plate or tube current. The divergent slit which meters the X-ray beam from the tube has 4 of arc. The receiving slit between the source and the sample has an aperture of 0.006 inch. These provide a nearly point source of X-rays for impingement upon the specimen. The scatter slit had an opening of 4, this being the slit which allows acceptance of the reflected and/or diifracted X-rays leaving the specimen. Scale F was used (1/8/1) with the time content of one. The receiving head assembly is rotated relative to the incident beam at a rate of 2 per minute. The strip chart is pulled past the pen at such a rate that 4 of receiver head movement occurs during each inch of chart movement (abscissa of the graph). The diagrams of FIGS. 1-3 were reduced to about one-half the original size.

Numerical values assigned to each peak represent the distance between paarllel planes Within the crystal in angstrom units. They are arrived at from Braggs Law using the equation D 2 sin 0 where h=wave length of the rays; D=distance between the atomic planes; and 0=angle of incidence of the rays.

The wave length of copper Ka is 1.54 A. and in this case the equation reduces to 1.54 D 2 sin 6 It will be observed that the diffractometer measures 20.

In FIG. l (the product of Test No. 3 of Example 2) all of the peaks are identified as due to TiOz present as rutile as the major component and anatase as the minor component. In FIG. 2 (the product of Test No. 2 of Example 2) it is evident that the product also contains TiOZ an rutile in significant amount. No barium sulfate as such was detected, indicating that the BaSO4 determined by assay was tied up in some form of a complex. There are a number of unidentified line which do not correspond to any calcium-silicon-oxygen compound. In FIG. 3 the product of Example 3) the diagram also indicates large amounts of Ti02 as rutile. BaSO-4 is the other major component of this material. Unidentied lines are also present. Those data indicate that in the case of FIG. 2 (80% TiO2) and FIG. 3 (38% Tio-2), the compounds are true complexes of CaO, SiOg and BaSO4 present together with the Ti02.

EXAMPLES 4-9 Referring to FIGS. 4 to 6 which illustrate the design and use of equipment suitable for making the complex compositions of Ti02 on a commercial scale, the followmg procedures were carried out in the apparatus shown. A portion of a casing of a suitable centrifugal pump 10 having an inlet 11, a discharge 12, and an impeller 15 rotating about an axis 16 is shown in FIG. 4. In FIG. 5 there is shown on an enlarged scale an inlet pipe 20 attached to the pump casing 10 at 21. Closely adjacent to the connection 21 there is a Y 22 having two branches 25 and 26. The pump may suitably be a closed impeller pump such as Ingersoll-Rand Motor Pump Model ZORVL-S having a capacity of 150 g.p.m. at a 52 ft. head, an impeller diameter of 11 inches, and a power input of 5 HP at 1150 r.p.m.

In carrying out the procedure of the invention, a solution A, which is the titanyl sulfate, and is at a temperature of F. is introduced at the inlet 11. Solution B introduced through the connection 21 is the alkaline solution at a temperature of 200 F. Following the procedure described in Example 1 the following additional Examples 4, 5, 6, 7, 8 and 9 were carried out by simultaneously introducing an acid titanyl sulfate solution at 11 and a mixture of sodium hydroxide solution and barium chloride solution through the Y connection 22 above. Pigment E was the 80% TiOz pigment prepared in Example 2, Test 2.

Each of the pigments A through E after being wetground in a ball mill was made up in the following conand into the pipe connection 20. In Example 9 no BaClZ 5 centrations: was added. A product consisting of a slurry of the pre- 0 01 A, cipitated pigment in the aqueous mother liquor was re- 0'05 gm/ter moved from the pump at 12 and treated to separate the 01 gni/liter precipitated pigment, after which it was dried and calolg gum/litter cined as described above. The products of Examples 4 10 gm' er to 9 contained the following respective amounts of TiOz These were then measured on the Bausch & Lomb spes (the femalllder being C30, S102 and 1321304): 100%, tronic 20 colorimeter at 500 microns Wavelength. 95%, 80%, 5%, 40% and 40%. The reaction conditions Standard Bausch & Lomb selected test tubes were used and the properties of the product are set forth in the to contain the dispersions during all measurements. The following table. 15 results of such measurements are plotted on FIG. 7 which TABLE II Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Final titanium dioxide, complex mixture 100% TiOz 95% TiOz, 80% T102, 5% T102, 40% TiOz, 40% T102, 60% added (No complex) 5% added 20% added 95% added 60% added (No barium) For 100 For 150 For 100 For 100 For 150 For 100 For 100 For 150 For 100 For 150 Amounts of chemicals used lbs. TiOz gpm. lbs. T102 lbs. T102 gpm. lbs. TiOz lbs. TiOz g.p.m. lbs. TiO2 g.p.m. in preparation (according to calcined produeealcined calcined produccalened calcined produecalcined producsystem given to the right) yield tion yield yield tion yield yield tion yield tion Titanyl sulfate (0.1060 gms.

Flog/1111.); gallons 113 9. 0 113 113 9. 0 113 113 9. 0 113 9. 0 Dilution Water for titanyl sulfate; gallons 087 81 987 987 81 987 087 8l 987 81 Sodium silicate:

Dry Na3-8 S102 (lbs.) 3. 7 17. 8 1. 5 1, 352 107 8. 8 114 17.6 Gallons of 18 75% solution 2. 4 11. 5 0. 95 873 60 5. 7 138 11. 4 Calcium chloride:

Dry CaClg (pounds) 0. 97 4. 7 0.39 354 28 2. 3 56 4.6 Gallons of 10% solution 1. 2 5. 7 0. 47 437 34. 5 2. 8 69 5.6 Barium chloride:

Dry BaClg (pounds) 2. 3 11. 1 0. 03 843 66. 6 Gallons of 10% solution 2. 8 13. 5 1. 1 1, 025 81 Sodium hydroxide:

Dry NaOH (p0unds) 1, 200 100 1, 200 1, 200 100 1, 200 1, 200 Gallons of 5 normal solution 720 720 720 60 720 720 Total yield (pounds);

complex:

HgTiOs 123 10. 1 123 123 10. 1 123 123 10. l 123 10. 1 BaSO4 2. 6 12. 5 1.02 950 75 6. 17 Cao-4 Si02-3 H2O 3. 1 14. 9 1. 22 l, 132 89. 4 7. 35 178. 6 15. 7 Calcincd yield (pounds) complex:

i0; 100 8. 23 100 100 8. 23 100 100 8. 23 100 5. 23 BaSO4 2. 6 12. 5 1. 02 950 75 6. 17 08.0.4 SiOz 2. 6 12. 5 1. 02 950 75 6. 17 150 12. 34

EXAMPLE 10 Aqueous suspensions were prepared from a number of pigments and the percentage of transmission of light at 500 microns was measured for each such suspensions to determine the opacity of each of the particular pigments. Pigment A was an Anatase pigment of a commercial grade known as RAYOX RG. It had an average particle size of about 0.25 micron. Pigment B was a type of clay sold commercially under the name Sprayis a semi-log graph as a function of the concentration of the particular dispersion.

It has been established that relatively dilute suspensions of titanium dioxide pigments follow the Beer-Lambert Law, Le., the relationship between the logarithm of the light transmitted through the dispersion and the concentration of the dispersion is a straight line over the measurable limits of the instrument. Therefore, by plotting the logarithm of the percent transmittance versus the concentration, a straight line is obtained. All the lines extrapolated to one common point transmission at zero percent pigment dispersion). The curves with the greater slope have the greater opacity per unit of pigment (since they allow less transmission). The relative opacitying powers of the pigments, therefore, can be determined by measuring the relative slopes of the curves as shown in FIG. 7. It will be observed from FIG. 7 that the prod- 1 1 uct of Examples 2 and 3, that is those containing 80% TiO2 and 38% Ti02, respectively, had a significantly better opacity than pure Anatase and clay. Sample C, which was 100% Ti02 prepared by the procedure of Example 2, also showed a significantly higher opacity than the pure Anatase.

Although the uses of the compositions and methods of the invention have been illustrated in connection with the manufacture of paper, they are also useful in the manufacture of elastomeric products such as rubber as a pigment and/or ller, in the manufacture of paint as a pigment and/or extender, and in still other products.

I claim:

1. In the process of precipitating H2Ti03 from acid solutions of titanyl sulfate by the use of alkaline solutions, followed by calcining to obtain rutile TiO2, the improvement which comprises introducing said titanyl sulfate solution into a high shear zone adjacent a rapidly rotating impeller, simultaneously introducing into said zone an aqueous alkaline solution of an alkali metal in an amount suicient substantially at least to neutralize said titanyl sulfate solution, mixing said solutions in said high shear zone to precipitate H2Ti03, said titanyl sulfate solution prior to said mixing being substantially free of premature thermal hydrolysis, the extent and intensity of said high shear being sutlicient to produce particles of precipitated H2Ti03 which, upon calcining at a temperature from 400 to 2200 F. produce rutile Ti02 particles in the range of about 0.2-0.25 micron, the temperature of said mixed solutions being about 100-212 F. and the pH of said mixed solutions being about 8-10, withdrawing from said zone effluent containing said precipitated HzTiOS, removing said H2Ti03 from its mother liquor, and drying the H2Ti03.

2. A method of claim 1 in which said titanyl sulfate solution and said alkaline solution are mixed in the high shear zone adjacent the impeller of a centrifugal pump by contnuously introducing said solutions to said zone.

3. A method of claim 1 in which said titanyl sulfate solution is kept below its hydrolysis temperature until it reaches said high shear zone.

4. A method of claim 1 in which the temperature of said mixed solution is at least about F.

5. A method of claim 1 in which said aqueous acid solution of titanyl sulfate prior to said mixing is maintained below about 170 F. to avoid premature thermal hydrolysis.

6. A method of claim 1 in which said dried H2Ti03 is calcined at a temperature from 400 to 2200J F.

7. A method of claim 1 in which said dried H2Ti03 is calcined at a temperature between about 1600 and 1800" F.

References Cited UNITED STATES PATENTS 1,504,670 8/ 1924 Blumenfeld 23-202 RX 1,758,528 5/ 1930 Mecklenburg 23-202 R 2,316,840 4/ 1943 Cole 23-202 R 2,350,095 5/1944 Carlson 210-2 3,180,699 4/1965 Ballestra 23-1 R 3,341,291 9/1967 Mabbs et al 23-202 3,347,620 10/1967 Yamashita 23-1 3,412,944 11/ 1968 Wollenberg 23--202 RX 3,418,074 12/ 19168 Sargeant 23-202 RX OTHER REFERENCES J. Barksdales book Titanium, 1949 ed., pp. 64, 65, 73 and 74, The Ronald Press Co., New York.

I. Barksdales book Titanium, 1966 ed., pp. 78, 79', 87-90, The Ronald Press Co., New York.

Chemical Engineers Handbook, 1950 ed., John H. Perry, editor, pp. 1196-1198, 1204, McGraw-Hill Book Co., New York.

Chemical Abstracts, vol 56, May 19162, p. 10989.

EDWARD STERN, Primary Examiner U.S. Cl. X.R. 

